This invention relates to perfluoroalkyl-substituted amines, acids, amino acids and thioether acids and their salts that are useful as surfactants in a wide variety of applications.
Perfluoroalkyl (xe2x95x90RF) substituted water soluble compounds are used primarily as specialty surfactants which can lower the surface energy of aqueous media to well below 20 dynes/cm, as compared to 25 dynes/cm for silicone based surfactants and 30 dynes/cm for conventional hydrocarbon surfactants. They are therefore useful in applications where conventional hydrocarbon and silicone-based surfactants fail, such as in coating of low free-energy surfaces such as polyolefins and oil-contaminated surfaces. RF-surfactants also allow the formulation of aqueous fire-fighting systems that can be used against organic solvent fires, such as those involving burning gasoline or alcohols. Such surfactant formulations are described in U.S. Pat. Nos. 4,460,480 and 5,218,021.
While fluorosurfactants as a general rule contain only one RF group per molecule, compounds with 2 or more RF groups are useful for grease-proofing paper products used, for example in the fast food industry. Typical compounds are described in U.S. Pat. Nos. 4,419,298; 4,536,254; and 5,091,550. Typical di-RF-compounds derived from amino acids, allyl glycidyl ether (AGE) and perfiuoroalkyl iodides are described in U.S. Pat. No. 5,491,261.
Canadian Patent 983,929 describes mono RF-substituted cationic surfactants made by reaction of an RF-iodide with, first, allyl glycidyl ether (AGE), secondly, with amines and alkanolamines. No carboxylic acids or sulfonic acids are described therein.
U.S. Pat. No. 4,038,195 describes RF-surfactants useful for aqueous fire fighting foams that are derived from glycine and N-methylglycine (sarcosine) by reaction with an RF-oxirane prepared from allyl glycidyl ether and an RF-iodide and followed by dehydrohalogenation. In this patent it is taught that the ensuing double bond improves the linearity of the molecule and its performance.
It has now been discovered that a large variety of 3-perfluoroalkyl-(2,3-ene or 2-iodo) propyl-substituted amino acids as well as thioether acids and their salts, which can be made by reaction of amines or amino acids, or of thio acids with allyl glycidyl ether, followed by reaction with a perfluoroalkyl iodide and partial or complete dehydrohalogenation and, optionally, quaternization, are excellent surfactants. They can be prepared in high yields and are useful as aqueous surfactants in a variety of applications where low surface tensions are required, including coating formulations for glass, wood, metal, cement, paper and textile materials, as active ingredients in hard surface (glass, plastic, metal, stone, laminates, etc.) cleaning products, as well as additives to dye baths, liquid laundry detergents and cosmetic products for the hair and skin, as foam control agents in polyurethane foams and especially as components in aqueous fire-fighting formulations.
The presence of the more hydrophobic 3-perfluoroalkyl-2-iodopropyl intermediate resulting from partial dehydrohalogenation may actually benefit the overall surface tension. According to Jarvis (J. Phys. Chem. 64, 150 (1960), the solubility of a fluorochemical has a significant effect on surface activity. An increase in the organophobic part of the molecule decreases the surface tension while the solubility of the molecule also decreases. Eventually, inadequate solubility of the molecule limits the minimum surface tension that can be achieved.
The present invention provides 3-perfluoroalkyl-(2,3-ene and/or 2-iodo) propyl-substituted amines, amino carboxylic and sulfonic acids, and thioether carboxylic, phosphoric, sulfonic and sulfuric acids, and salts and quaternized derivatives thereof, which are prepared from the corresponding amines, amino and thioether acids by reaction with allyl glycidyl ether and perfluoroalkyl iodides, followed by partial or complete dehydrohalogenation.
Another aspect of this invention relates to a substrate which contains, or has been treated with, 0.01 to 10% by weight of a fluorine-containing composition, at least part of said fluorine being provided by one of the compounds according to the present invention.
Another aspect of this invention relates to fluorine-containing aqueous fire-fighting compositions, at least part of said fluorine being provided by one of the compounds according to the present invention.
The novel perfluoroalkyl amines, amino acids and thioether acids of the present invention are of the formula:
QFxe2x80x94NR1R2xe2x80x83xe2x80x83(Ia),
QFxe2x80x94N(xe2x86x92O)R1R2xe2x80x83xe2x80x83(Ib),
QFxe2x80x94N+R1R2R3Axe2x88x92xe2x80x83xe2x80x83(Ic),
QFxe2x80x94Sxe2x80x94R4xe2x80x94COOMxe2x80x83xe2x80x83(IIa),
QFxe2x80x94S(O)2xe2x80x94R4xe2x80x94COOMxe2x80x83xe2x80x83(IIb),
QFxe2x80x94SO3Mxe2x80x83xe2x80x83(IIIa),
QFxe2x80x94NR1xe2x80x94(PO3)3Mxe2x80x83xe2x80x83(IIIb)
or
QFxe2x80x94NR1xe2x80x94SO3Mxe2x80x83xe2x80x83(IIIc),
in which
R1 is an aliphatic, aromatic or cyclo-aliphatic hydrocarbon residue with one to 20 carbon atoms, optionally interrupted by one or more oxygens and/or substituted by hydroxy groups, or is R2;
R2 is R1 or an aliphatic, aromatic or cyclo-aliphatic hydrocarbon residue with 1 to 20 carbon atoms, substituted by one or two carboxy groups or a sulfate or a sulfonate group, and which is optionally further substituted by amino or hydroxy groups and/or interrupted by tertiary amino groups, sulfur or oxygen, with the proviso that when R2 is R1, the compound is of structure (1b) or (1c), and when R2 is xe2x80x94CH2xe2x80x94COOH, QF is QF1;
R3 is C1-C5alkyl or benzyl, or is a C1-C5alkylene group which is substituted by a carboxy or sulfonate group;
R4 is C1-C5alkylene or phenylene;
Axe2x88x92 is an ionically or covalently bound anion;
M is hydrogen, an alkali metal cation, ammonium, or ammonium that is mono-, di-, tri- or tetra-substituted by C1-C4alkyl, C1-C4-hydroxyalkyl, or a mixture thereof; and
QF is 0 to 50% by weight QF1 and 50 to 100% by weight QF2, wherein
QF1 is RFCH2CHIxe2x80x94CH2xe2x80x94Oxe2x80x94CH2CH(OH)CH2xe2x80x94 and
QF2 is RFCHxe2x95x90CHxe2x80x94CH2xe2x80x94Oxe2x80x94CH2CH(OH)CH2xe2x80x94,
in which
RF is a monovalent, perfluorinated, alkyl or alkenyl, linear, branched or cyclic organic radical having three to twenty fully fluorinated carbon atoms, which organic radical is optionally interrupted by divalent oxygen or sulfur atoms,
with the proviso that the compound of the formula 
is excluded.
Axe2x88x92 as an anion is for example an acetate, a halide such as a chloride, bromide or iodide, or is a covalently bound carboxyl or sulfonate group. Axe2x88x92 is in particular a chloride or a covalently bound carboxyl group.
M as an alkali metal cation is, for example, a cation of sodium, lithium or potassium. M as an alkali metal cation is especially a cation of sodium.
When M is ammonium that is monosubstituted by C1-C4alkyl, it is, for example methyl-, ethyl-, n-propyl-, isopropyl-, n-butyl- or tert.-butylammonium.
When M is ammonium that is disubstituted by C1-C4alkyl, it is, for example dimethyl-, diethyl-, di-n-propyl-, diisopropyl-, or di-n-butylammonium.
When M is ammonium that is trisubstituted by C1-C4alkyl, it is, for example trimethyl- or triethylammonium.
When M is ammonium that is tetrasubstituted by C1-C4alkyl, it is preferably tetramethyl-, tetraethyl-, methyltributyl- or tetrabutylammonium.
When M is ammonium that is mono-, di-, tri- or tetra-substituted by C1-C4hydroxyalkyl, it is, for example diethanol-, disopropanol- or triethanolammonium, with diethanol- or triethanolammonium being particularly preferred.
M as a mixture of C1-C4alkyl and C1-C4-hydroxyalkyl is, for example methylethanolammonium.
M is in particular an ammonium or sodium cation.
The perfluoroalkyl moiety RF may be a single perfluoroalkyl group, for example perfluorohexyl, or a mixture of such groups, for example a mixture of C4F9xe2x80x94, C6F13xe2x80x94, C8F17xe2x80x94, C10F21xe2x80x94, C12F25xe2x80x94 and C14F29xe2x80x94 groups.
Preferred compounds according to the present invention include those wherein QF is 80 to 100% by weight of QF2, and RF is saturated and contains 6 to 18 carbon atoms, is fully fluorinated and contains at least one terminal perfluoromethyl group. Most preferably, RF is a fully fluorinated, linear carbon chain with an average of about 6 to 10 carbon atoms.
Preferred compounds of formula (Ia) include those wherein R1 is C1-C4alkyl and R2 is a radical residue of a naturally occurring amino acid with two or more hydrocarbon atoms, or of p-amino-benzoic acid, aminomethane sulfonic acid, taurine or beta-alanine.
Particularly preferred compounds of formula (Ia) include those wherein R1 is methyl and R2 is xe2x80x94CH2xe2x80x94CH2xe2x80x94COOH or xe2x80x94CH2CH2xe2x80x94SO3H.
Preferred compounds of formula (Ic) include those wherein R1 and R2 are C1-C4alkyl, R3 is C1-C5alkyl or benzyl, and Axe2x88x92 is chloride.
Additional preferred compounds of formula (Ic) include those wherein R1 and R2 are methyl, R3 is xe2x80x94CH2xe2x80x94COOxe2x88x92, and Axe2x88x92 forms a betaine with the quatemary nitrogen.
Preferred compounds of formula (IIa) include those wherein R4 is xe2x80x94CH2CH2xe2x80x94, xe2x80x94CH(COOH)CH2xe2x80x94 or xe2x80x94C(COOH)xe2x95x90CHxe2x80x94.
Preferred compounds of formula (IIb) include those wherein R4 is xe2x80x94CH2CH2xe2x80x94.
Also preferred are compounds of formula (IIIb) and (IIIc) wherein R1 is C1-C4alkyl, especially methyl, for example the compounds QFxe2x80x94N(CH3)xe2x80x94(PO3)3H and QFxe2x80x94N(CH3)xe2x80x94SO3H.
The compounds of formulae (Ia), (Ib), (Ic), (IIa) and (IIb) of this invention may be synthesized by first reacting allyl glycidyl ether with a primary or secondary amine to introduce at least one allyloxy radical, then adding an RF-iodide to the resulting allyloxy radical, followed by partial or complete dehydrohalogenation.
Compounds of formulae (IIa), (IIIb) and (IIIc) of this invention may be prepared by first adding allyl glycidyl ether to a mercapto acid to introduce an allyloxy radical, followed by addition of RF-iodide to the allyloxy radical, followed by partial or complete dehydrohalogenation. Interesting allyloxy compounds can be synthesized for example by addition of equimolar amounts allyl glycidyl ether (=AGE) to amines such as dimethylamine or sarcosine (N-methyl-glycine), or by addition of allyl glycidyl ether to mercaptans such as mercaptopropionic acid.
The addition of the RF-iodide to the allyloxy alcohols or acids proceeds readily in the presence of a free radical initiator such as an azo compound or peroxide at conventional initiation temperatures of 35 to 150xc2x0 C. It was found, however, that only in the presence of sulfite, bisulfite or dithionate ions does the reaction proceed fast enough and conversions are high enough to make the synthesis commercially practical. The novel process to make the compounds of this invention is described separately in U.S. Pat. No. 5,585,517 and in co-pending application Ser. No. 09/691,486.
A solvent can be present during the reaction. Useful solvents include for example ketones such as acetone, methyl ethyl ketone or methyl-propyl ketone, esters such as isopropyl acetate, alcohols such as ethanol or butanol, ethers such as dioxane or di-(2-hydroxyethyl)-ether, hydrocarbons such as toluene or octane, amides such as dimethylformamide and lactams such as N-methylpyrrolidone, and mixtures thereof.
Complete dehydrohalogenation is generally carried out in water at 50 to 100xc2x0 C. in the presence of a strong base such as sodium or potassium hydroxide, over a period of several hours. If the product is obtained as the non-aqueous phase, it is repeatedly washed with water and finally isolated, either as a melt, by filtration or as a solution, depending on the specific product. The dehydrohalogenated product is analyzed for its hydroxyl value prior to further reaction. The trans/cis ratio is typically 85/15 according to NMR analysis. The trans isomer can be selectively obtained by employing a hindered amine base such as DABCO(trademark) or a trialkylamine.
The compounds of the present invention are useful as surfactants in a variety of applications where a low surface tension is required, including coating formulations for glass, wood, metal, brick, concrete, cement, natural and synthetic stone, tile, synthetic flooring, paper, textile materials and plastics. In waxes and polishes for floors, furniture, shoes, automotive care and other types of hard surfaces, they improve wetting, leveling and gloss.
They are useful as active ingredients in a variety of cleaning products for hard surfaces such as glass, tile, marble, ceramic, linoleum and other plastics, metal, stone, laminates, etc. They are especially useful to achieve wetting of otherwise difficult to wet surfaces, such as oil-contaminated metals and polyolefins. Thus one aspect of this invention relates to a wetting composition, which comprises at least one compound of the present invention and a liquid carrier, and to a method of wetting a surface, which comprises contacting the surface with said wetting composition.
Their ability to wet metals makes the compounds of the present invention useful as additives for solvent cleaning and scale removal of metals and metal equipment, for metal pickling baths to increase life and acid runoff, for chrome electroplating, where they reduce surface tension and foaming and as additives for soldering flux, especially for electronic circuitry.
To wet low energy surfaces including natural and synthetic rubbers, resins and plastics, the surfactants of the present invention can be employed in synergistic mixtures with hydrocarbon surfactants.
Compounds of the present invention are also useful as wetting agents for compositions containing herbicides, fungicides, weed killers, hormone growth regulators, parasiticides, insecticides, germicides, bactericides, nematocides, microbiocides, defoliants or fertilizers, where they aid in wetting the surface the composition is applied to and, in the case of an insecticide, enhance its penetration into the insect. Likewise, in the pharmaceutical industry, the compounds of the present invention are useful to enhance penetration of therapeutic agents such as antimicrobials through the skin. They are also useful to improve the strength and homogeneity, and to reduce the permeability of encapsulated materials. They may also be used to emulsify fluorochemical blood substitutes.
The surfactants of the present invention can be incorporated into products that function as antifogging agents for glass surfaces exposed to humid atmospheres such as mirrors in bathrooms, automobile windshields and eyeglasses. These fluorosurfactants may also be incorporated into products to function as an antistatic agent for magnetic tapes, phonograph records, floppy disks, disk drives, rubber compositions, PVC, and to reduce the surface charge of polyester film.
The compounds of the present invention are also useful as foam control agents in polyurethane foams. Thus another aspect of this invention relates to a method of controlling foam during polyurethane foam manufacture, which comprises incorporating an effective foam-controlling amount of a compound according to the present invention into a polyurethane foam formulation.
They are also useful in controlling foam in other products such as spray-on oven cleaners, foamed kitchen and bathroom cleansers and disinfectants, and in aerosol shaving foams.
They are also useful in controlling foam in textile treatment baths, as a wetting agent for finish-on-yarn uniformity and as a penetrating agent for finishes on tow, heavy denier fibers.
Their ability to promote wetting and penetration makes the compounds of the present invention also useful in a variety of personal care products for hair, like shampoos, conditioners and creme rinses where they ensure even deposition of other actives as well as improve the lubricity of the hair to facilitate wet-combing. Additionally they are useful in cosmetic products for the skin such as therapeutic or protective creams and lotions, oil and water repellent cosmetic powders, deodorants and anti-perspirants, nail polish and lipstick. Compounds according to the present invention can also be used advantageously in toothpastes containing potassium fluoride to enhance fluoroapatite formation and inhibit caries. In combination with a nonionic fluoroalkylamide synergist in toothpaste, they can increase enamel-fluoride interactions.
Additionally they are useful adjuvants to household care products such as floor and furniture waxes and polishes, and to fabric care products such as stain pretreatments and/or stain removers for clothing, carpets and upholstery, as well as in laundry detergents. They are also useful as a rinse-aid for car washes and in automatic dishwashers.
Compounds according to the present invention are also useful in dry cleaning, where they improve soil suspension in perchloroethylene and reduce redeposition. They are also useful for improved wetting and leveling and as an anti-cratering adjuvant for finishes and paints.
In the plastics and rubber industry, in addition to the uses described above, compounds of the present invention also useful as emulsifying agents for polymerization, particularly of fluoromonomers, and to aid in the preparation of agglomerates of powdered fluorocarbon polymers. They are also useful as latex stabilizers, as mold release agents for silicones, etc. and as additives for elimination of trapped air in plastic laminates.
In the petroleum industry the compounds of the present invention are useful as wetting assistants for oil well treatments, drilling muds and additives to improve tertiary oil well recovery, as well as in extreme pressure EP lubricants and as a lubricating cuffing oil improver, to improve penetration times.
In the graphic arts the compounds of the present invention are also useful as wetting agents for writing inks and as printing ink additives for ink flow and leveling in both aqueous and solvent based systems. They are also useful to form ink-repellent surfaces for waterless lithographic plates and electrographic coatings. In photography the compounds of the present invention are useful as photoemulsion stabilizers, coating aids in the preparation of multiple layer film elements, as antifogging agents for films and antistatic wetting agents for film coatings as well as surfactants for developer solutions.
The compounds of the present invention are also useful as wetting agents for fighting forest fires, as a component of fluoroprotein foams, as additives to dry chemical extinguishing agents and as agents in aerosol-type extinguishers. But they are especially useful as components in aqueous fire-fighting foam formulations. Aqueous fire-fighting formulations are described for example in U.S. Pat. Nos. 4,038,195 and 5,496,475, the disclosures of which are incorporated by reference. Thus another aspect of this invention relates to fluorine-containing aqueous firefighting compositions, wherein at least part of the fluorine is provided by at least one compound according to the present invention.
Another aspect of this invention is a substrate comprising 0.01 to 10% by weight of a fluorine-containing composition, at least part of said fluorine being provided by a compound of the present invention.
The compounds of the present invention are generally applied to a substrate as a dilute aqueous phase. A typical application level is in the range of 0.01 to 0.2% by weight of a compound of the present invention based on the aqueous phase.
The following examples describe certain embodiments of this invention, but the invention is not limited thereto. It should be understood that numerous changes to the disclosed embodiments could be made in accordance with the disclosure herein without departing from the spirit or scope of the invention. These examples are therefore not meant to limit the scope of the invention. Rather, the scope of the invention is to be determined only by the appended claims and their equivalents. In these examples all parts given are by weight unless otherwise indicated.